A reaction mechanism for the polymerization of 1,3‐propanediol is proposed for two acid catalysts. Population and mass balance equations are derived for small molecules and for polymeric species of chain distributions distinguishable in terms of protonation state and end group functionality. Since the sulfuric acid catalyzed process has two types of polymer linkages, the derivation of the moment equations is challenging. The reverse reactions are also accounted thus creating a moment closure problem. A mass transfer model is developed to predict reaction mixture water content. The Sanchez‐Lacombe equation of state is used to calculate phase behavior and species partitioning. Optimization of selected parameters is accomplished by comparison to laboratory data resulting in a fully predictive model.
Manufacturers typically sell consumer products through retailers and the presence of intermediaries has interesting ramifications for their product variety and pricing decisions. Retailers may want higher variety to help reduce price competition but the costs of variety are borne by the manufacturer. The increased variety may increase demand and profits for the manufacturer too but this depends on market-specific factors as well as costs. We explore these interactions through a model wherein a manufacturer sells multiple product variants at a wholesale price to two retailers who in turn compete for consumers. Consumers choose between the retailers based on the price and variety offered by each retailer and the search or transportation cost incurred by the consumer, equivalent to the level of retailer differentiation in our model. Several insights emerge from the analysis. The manufacturer offers the same variety to both retailers and this variety increases with market size and consumer sensitivity to variety. We find that some retailer differentiation benefits the retailers (not the manufacturer) but too much differentiation hurts both the retailers and the manufacturer. If the market is fully covered, then the channel is coordinated even with a simple wholesale pricing contract. If the retailers incur costs to sell the product, the manufacturer surprisingly loses out more than the retailers and in fact absorbs some or all of the retailer costs. Finally, asymmetry between retailers has some unexpected consequences. For example, variety is not impacted by asymmetry in consumer preferences for a retailer and the manufacturer offers the same variety to both retailers. 相似文献
The conformations of protonated RA15K, RA20K and RA15H (R = arginine, A = alanine, K = lysine, and H = histidine) have been examined in the gas phase as a function of temperature. These peptides were designed so that intramolecular proton transfer will trigger conformational changes between a helix (proton sequestered at the C-terminus) and globule (proton sequestered at the N-terminus). Kinetically controlled structural transitions occur below 400 K (from helix to globule for RA15H, and from globule to helix for RA15K and RA20K). As the temperature is raised, the compact globule found at room temperature expands, accesses more configurations, and becomes entropically favored. At around 500 K, the RA15K and RA20K helices undergo a melting transition. The transition is broad, as expected for a phase transition in a finite system, and becomes narrower as the peptide size increases. In the helical conformation, the two basic residues are well separated; as a result, the proton transfer necessary to drive the melting transition probably involves a mobile proton. For doubly protonated RA15K, a dumbbell-like conformation (resulting from repulsion between the two protonated basic residues) is found at high temperature. 相似文献
ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option. 相似文献